Preparation of amino derivatives of the anthraquinone series



Patented Aug. 22, 1933 UNITED STATES PREPARATION OF AMINO DERIVATIVES OFTHE ANTHRAQUINONE SERIES Philip H. Groggins, Washington, D. 0.,dedicated to the free use of the public, of and within The United Statesof America No Drawing. Application July 30, 1932 Serial No. 627,116

13 Claims.

(Granted under the Act of March 3, 1883, as amended April 30, 1928; 3700. G. 757) This application is made under the act of March 3, 1883, asamended by the act of April 30, 1928, and the invention hereindescribed, if patented, may be manufactured and used by or for theGovernment, for governmental purposes,

' without payment to me of any royalty thereon.

I hereby dedicate the invention herein described, to the free use of thepublic, of and within the United States of America, to take effect uponthe granting of a patent to me.

This invention relates to the preparation of carbon compounds and moreparticularly to the preparation of amino derivatives of theanthraquinone series. It especially contemplates the ammonolysis ofhalogeno anthraquinones.

The invention has for an object the preparation of amino-anthraquinonesby new chemical processes.

Other objects are the preparation of these compounds in a very purestate in high yields, by processes which are simple and which may bereadily carried out, and which are beyond the purview of my co-pendingapplication for patent, Serial No. 548,043, filed June 30, 1931, which 5points out the advantage of using chlorates and nitrates as oxidants.

These objects are accomplished by the heating of halogeno-anthraquinoneswith strong aqueous solutions of ammonia under pressure in the presenceof oxyhalogen compounds. The invention also contemplates the optionaluse of a catalyst or an alkali metal nitrate.

The invention will befurther understood from a consideration of thefollowing examples, in

which the parts are given by weight:

EXAMPLE I Preparation of beta-amino-anthraquinone In a suitable highpressure autoclave there was placed 36.5 parts of2-chloro-anthraquinone, .72 parts of cupric nitrate, and 1.6 parts ofpotassium iodate. Thereafter 315 parts of 28% aqueous ammonia were addedand the autoclave closed. The charge was heated to gradually raise thetemperature to 195 C. This temperature was maintained for approximately24 hours, after which the reaction mass was filtered and the solidmaterial washed free from the mother liquor. Z-aminQ-anthraquinone of97.5% purity was obtained. The yield was 95 of the theoretical. EXAMPLEII Preparation of beta-amino-anthraquinone To a mixture of 36.5 parts ofbeta-chloroanthraquinone, 2 parts of ammonium nitrate, 2 parts of sodiumbromate in an autoclave'there was added 320 parts of 30% aqueousammonia; After closing the autoclave the resultant mix 'ture was heatedin such a manner'that 'the temperature was gradually raised to 195 C.This temperature was maintained for twenty-four hours. The reaction masswas thereafter transferred to a distillation apparatus, made alkaline 5with sodium hydroxide, and the excess of ammonia recovered bydistillation. The residue remaining in the still was thereafter filteredand washed freefrom the mother liquor. The solid product obtained wasbeta-amino-anthraquin- 7() one having a purity of 96%. The yield was 896% of that theoretically possible. The amino compound gave a cleardiazonium salt solution.

EXAMPLE III Preparation of alpha-amino-anthraquinoneAlpha-chloro-anthraquinone was treated by the process set out in ExampleII with equally desirable results.

The invention is not limited to the exact details given in the aboveexamples. In general the various chlorine substituted anthraquinonederivatives may be used satisfactorily. The results obtainable by usingas starting substances such compounds as 1-nitro-5chloro-anthraquinone,1-nitro-6chloro-anthraquinone, l-nitro- '7-chloro-anthraquinone, 1 nitro8chloro-anthraquinone, beta-chloro-anthraquinone,alphachloro-anthraquinone, 1: 5 di chloro-anthraquinone, 1:8-di chloroanthraquinone, 2:6-dichloro-anthraquinone, 2 '7 di chloro-anthraquinoneand the various nitro-di-chloro-anthraquinones, merit special mention.

The temperatures at which the processes of this invention are carriedout, as will be obvious to one skilled in the art, depend upon theparticular starting compound and the other ingredients of the reactionmass. In general the preferred temperature range is between C. and 2250.

In carrying out my process any inorganic oxyhalogen compound may beused. This class comprises the salts of hydrochlorous acid HOCl,perchloric acid H0104, and chloric acid I-IClOs as well as thecorresponding iodine, bromine, and fluorine compounds. It furthercontemplates the use of the halogen gases since these react to formhypohalogen compounds with aqueous ammonia.

Because of its availability, alkali metal chlorates are generally used,but it is to be understood that the corresponding salts of otherinorganic halides such as iodat'es, bromates, etc. give equivalentresults.

In the examples ammonium nitrate has been use. This may be replaced withother alkali metal nitrates, for example, sodium nitrate.

The strength of the aqueous ammonium solution may be varied, butpreferably the concen- I tration is that corresponding to a 20 to 50%ammonia (NI-I3) content. With decreasing concentration of the ammoniasolution increasing temperatures may be used advantageously.

In general, for a given concentration of ammonia the use of highertemperatures results in completion of the reaction in a shorter time.

This invention is applicable to halogeno-anthraquinones in general.Bromo-anthraqulm ones'also give very desirable results.

The invention is not limited to the use of metallic copper nor anyparticular copper salt as a catalyst. Other metals or metal salts, forinstance, the salts of the metals or the metals themselves which followcopper in the electromotive series are used advantageously. Specialmention may be made of copper nitrate, cupric oxide and silver chloride.

By the term reduced copper it is intended to cover metallic copper inany physical form, preferably precipitated copper in the form of a finecopper powder or sponge.

Throughout the specification and claims Where the term alkali metal isused it is intended to cover the ammonium radical (NH4 because it reactssimilarly to the corresponding sodium and potassium compounds.

The process of this invention has several Very important and distinctadvantages over any other processes known to the prior art. Among thesemay be mentioned the fact that the yields of amino-anthraquinonesobtained are substantially theoretical, the products of the process areso pure as to render unnecessary special or additional purificationsteps, the processes may be carried out at lower temperatures thanheretofore deemed possible, and the quantities of materials per chargecan be greatly increased in proportion to the ammonia content of theautoclave. This last mentioned advantage is of particular importance incommercial processes.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsthereof except as defined in the appended claims.

I claim:

1. A process which comprises heating halogeno-anthraquinone with aqueousammonia in an autoclave under pressure in the presence of an oxyhalogencompound and ammonium nitrate at a temperature of 150 C. to 225 C.

2. The process which comprises heating a halogeno-anthraqinone withaqueous ammonia in an autoclave under pressure in the presence of anoXyhalogen compound.

3. The process which comprises heating a chloro-anthraquinone withaqueous ammonia under pressure in the presence of an inorganicoxyhalogen compound.

4. The process which comprises heating a halogeno-anthraquinone withaqueous ammonia under pressure in the presence of an inorganic nitrateand an inorganic iodate.

5. The process which comprises heating a halogeno-anthraquinone withaqueous ammonia under pressure in the presence of an alkali metalnitrate and an alkali metal bromate.

6. The process which comprises heating a chloro-anthraquinone withaqueous ammonia under pressure in the presence of an oxyhalogen compoundwhich is soluble in aqueous am monia.

7. The process which comprises heating a chloro-anthraquinone with.aqueous ammonia under pressure in the presence of an alkali metalnitrate and an oxyhalogen salt which is soluble in aqueous ammonia.

8. The process which comprises heating a bromo-anthraquinone withaqueous ammonia under pressure in the presence of ammoniumni trate andan oxyhalogen compound.

9. The process which comprises heating a halogeno-anthraquinone withaqueous ammonia under pressure in the presence of an oxyhalogen compoundwhich is soluble in aqueous ammonia and a metal following hydrogen inthe electrochemical series.

10. The process which comprises heating a chloro-anthraquinone withaqueous ammonia under pressure in the presence of an.oxyhalo-. gencompound, and a copper containing catalyst.

11. The process which comprises heatinga halogeno-anthraquinone withaqueous ammoniav under pressure in the presence of an inorganicnitrate,an oxyhalogen compound, and a copper containing catalyst. I

12. The process which' comprises heating 'a halogeno-anthraquinone withaqueous ammonia under pressure'in thepresence of cupric nitrate, and anoxyhalo'gcn compound.

13. The process which comprises heating a bromo-anthraquinone withaqueous amr'nonia'inv a pressure system in the presence of an organicnitrate, an oxyhalogen compound, and a copper containing catalyst.

PHILIP H. GROGGINS.

